CN114477298B - Composite oxide and preparation method and application thereof - Google Patents
Composite oxide and preparation method and application thereof Download PDFInfo
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- CN114477298B CN114477298B CN202011162004.1A CN202011162004A CN114477298B CN 114477298 B CN114477298 B CN 114477298B CN 202011162004 A CN202011162004 A CN 202011162004A CN 114477298 B CN114477298 B CN 114477298B
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- composite oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- -1 inorganic acid salt Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 32
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000010936 titanium Substances 0.000 description 34
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 238000001354 calcination Methods 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 18
- 239000002002 slurry Substances 0.000 description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- DRWUOVOJVMEODA-UHFFFAOYSA-N 14-methylpentadecan-1-amine Chemical compound CC(C)CCCCCCCCCCCCCN DRWUOVOJVMEODA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229940115440 aluminum sodium silicate Drugs 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a composite oxide and a preparation method and application thereof. CeFe for the composition of the composite oxide x Ti y O δ‑α And is represented by x=5 to 35, y=1 to 25, and δ is a positive number representing a value when oxygen in the composite oxide reaches a valence state equilibrium, α=0 to δ/2. The method for producing the composite oxide includes a step of bringing a Ce source, a Fe source and a Ti source into contact and reacting the same to obtain the composite oxide. The composite oxide used as an oxygen carrier for chemical-looping hydrogen production has the advantages of high activity, good stability, high hydrogen yield and the like.
Description
Technical Field
The invention relates to a composite oxide and a preparation method and application thereof, in particular to a composite oxide and a preparation method thereof and application thereof in chemical looping combustion.
Background
The current industrial large-scale hydrogen production method mainly comprises the steps of natural gas steam reforming hydrogen production and coal gasification hydrogen production. The natural gas steam reforming hydrogen production is a strong endothermic reaction, part of fuel needs to be combusted to provide heat energy required by the reaction, the reaction is generally carried out in a tubular reactor (or a reformer tube), the hydrogen production efficiency per unit volume is low, a large-scale device needs to be built, and the equipment investment is high; the coal gasification hydrogen production is obtained by partial oxidation and gasification of coalThe obtained crude synthesis gas is subjected to shift reaction to obtain shift gas with high hydrogen content, and then is subjected to hydrogen purification after acid gas removal and purification to obtain industrial hydrogen. Pressure swing adsorption processes are often used for hydrogen purification, which can have a portion of the hydrogen lost. The carbon in the raw material of the hydrogen production process is finally CO 2 The method is characterized in that the method is discharged in a form, and the steam reforming hydrogen production and the coal hydrogen production are mixed with carbon dioxide with a small quantity in the exhaust gas, so that conditions are provided for CCS after separation is difficult. The development direction of the future large-scale hydrogen production technology is to be a novel hydrogen production method with the characteristics of high efficiency, high hydrogen purity and greenhouse gas emission reduction effect.
The chemical environmental protection hydrogen production technology is a novel and environment-friendly hydrogen production technology, and is a hydrogen production technology which utilizes oxygen atoms in an oxygen carrier to replace oxygen to oxidize fuel and simultaneously give consideration to hydrogen production. Based on redox reaction, a proper oxygen carrier is selected to alternately circulate between two reactors to prepare hydrogen, and the oxygen carrier reacts with methane, CO and other fuel in a fuel reactor to generate CO 2 And water vapor, carbon dioxide can be enriched through condensation and dehydration; in the oxidation reactor, the oxygen carrier is oxidized by water vapor and releases hydrogen. The method is an environment-friendly novel technology for carbon dioxide trapping and hydrogen production, and has great significance for solving the increasingly prominent problem of greenhouse gas emission and preparing clean energy source-hydrogen. Oxygen carriers and reactors are key points for chemical looping hydrogen production. The oxygen carrier generally adopts ferric oxide as an active component and is loaded on a carrier, the problem of carbon deposition caused by the reaction of the ferric oxide and the carbon-containing fuel at high temperature is serious, and the carbon trapping efficiency and the hydrogen production efficiency are influenced, so that the aspects of the oxygen carrier are still to be studied intensively.
CN106669685a discloses an oxygen carrier, a preparation method and application thereof. The preparation method comprises the following steps: (1) NaAlO of 2 Mixing NaOH, silica gel, cetyl Trimethyl Ammonium Bromide (CTAB), isohexadecylamine (CA), tetraethylammonium hydroxide (TEAOH) and water according to a certain proportion to form gel, and carrying out hydrothermal crystallization, drying and roasting on a gel system to obtain a material A; (2) Dispersing the material A prepared in the step (1) in distilled water to prepare a suspension, and adding dioxygen into the suspensionTitanium sol is filtered, dried and roasted to obtain a carrier; (3) And (3) loading lanthanum and/or cerium, nickel and/or cobalt on the carrier prepared in the carrier step (2) to prepare the oxygen carrier.
CN103374431a discloses an oxygen carrier, which is composed of CeO 2 -Al 2 O 3 As a carrier, niO is taken as an active component, and the carrier CeO 2 -Al 2 O 3 CeO in 2 Wrapping Al 2 O 3 Is of CeO 2 The content of NiO as active component in the oxygen carrier is 1-20%, preferably 1-10% and the pore diameter of the oxygen carrier is 10-100 nm.
CN102382706A TiO with cavity structure 2 Is a carrier, fe 2 O 3 TiO as active ingredient 2 Support and Fe 2 O 3 The mass percentage of the active ingredients is 50-95% and 5-50%.
CN101486941a provides a method for preparing an iron-based oxygen carrier, which uses iron nitrate and aluminum nitrate as raw materials, urea as fuel, and organically combines a sol-gel method with a combustion synthesis method to prepare nano-scale Fe with excellent anti-sintering performance 2 O 3 /Al 2 O 3 An oxygen carrier.
The oxygen carrier is used as a medium to circulate between the two reactors, and continuously transfers oxygen in the air (water vapor) reactor and heat generated by the reaction to the fuel reactor for reduction reaction, and the property of the oxygen carrier directly influences the operation of the whole chemical looping combustion/hydrogen production. Thus, the high performance oxygen carrier is realized with CO 2 The chemical looping combustion/hydrogen production technology with enriched characteristics is key. Currently, the oxygen carriers mainly studied are metal oxygen carriers, including Fe, ni, co, cu, mn, cd and the like, and the carriers mainly include: al (Al) 2 O 3 、TiO 2 、MgO、SiO 2 YSZ, etc., and also small amounts of non-metallic oxides such as CaSO 4 Etc. In the chemical looping combustion/hydrogen production process, the oxygen carrier is in a continuous oxygen-losing-oxygen-obtaining state, so the activity of oxygen in the oxygen carrier is very important. Relatively speakingThe oxygen carrier in the prior art has the defects of limited oxygen carrier rate, lower cyclic reactivity, incapability of bearing higher reaction temperature, low hydrogen production rate and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a composite oxide and a preparation method and application thereof. The composite oxide used as an oxygen carrier for chemical-looping hydrogen production has the advantages of high activity, good stability, high hydrogen yield and the like.
Composite oxide and CeFe for composition x Ti y O δ-α And is represented by x=5 to 35, y=1 to 25, and δ is a positive number representing a value when oxygen in the composite oxide reaches a valence state equilibrium, α=0 to δ/2.
In the context of the present specification, the term "value at which oxygen in the composite oxide reaches a valence equilibrium" means a value required for forming an electrically neutral composite oxide in which Ce is +3, fe is +3 or +2, ti is +4, O is-2, and α=0.
According to the present invention, x=5 to 35, preferably 10 to 30, more preferably 15 to 25, still more preferably 18 to 24.
According to the invention, y=1 to 25, preferably 3 to 20, more preferably 5 to 15.
According to the invention, α=0 to δ/2, preferably 0 to δ/4, more preferably 0.
According to the present invention, the composite oxide may be a supported composite oxide (also referred to simply as a composite oxide in this specification for convenience of description), that is, a composite oxide is supported on a carrier.
According to the invention, as the carrier, an inorganic refractory oxide is preferable. As the inorganic refractory oxide, for example, siO may be mentioned 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 、Al 2 O 3 -SiO 2 、CaO-SiO 2 And CaO-MgO-SiO 2 Etc., among which SiO is preferred 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 Or a combination thereof.
According to the present invention, the ratio of the complex oxide to the carrier is not particularly limited, but is generally 0.01 to 5:1, preferably 0.5 to 4:1, more preferably 1 to 3:1, by weight.
According to the present invention, the composite oxide can be produced by the following production method.
According to the present invention, the production method includes a step of bringing a Ce source, a Fe source, and a Ti source into contact and reacting them to obtain a composite oxide.
According to the present invention, the Ce source, the Fe source and the Ti source are used in a relative amount ratio such that the obtained composite oxide has a composition formula CeFe x Ti y O δ-α (α=0, hereinafter referred to as a composite oxide a), where x=5 to 35, y=1 to 25, and δ is a positive number, and represents a value when oxygen in the composite oxide reaches a valence equilibrium (as described above).
According to the present invention, x=5 to 35, preferably 10 to 30, more preferably 15 to 25, still more preferably 18 to 24.
According to the invention, y=1 to 25, preferably 3 to 20, more preferably 5 to 15.
According to the invention, α=0 to δ/2, preferably 0 to δ/4, more preferably 0.
According to the present invention, the contact method is not limited, and the Ce source, the Fe source, and the Ti source may be mixed with one another in a solution or a melt, for example, so long as they can react with one another to generate the composite oxide a.
According to the present invention, the contacting may be performed in the presence of a carrier, thereby obtaining a supported composite oxide a (also referred to as composite oxide a).
According to the invention, as the carrier, an inorganic refractory oxide or a precursor thereof is preferable. As the inorganic refractory oxide, for example, siO may be mentioned 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 、Al 2 O 3 -SiO 2 、CaO-SiO 2 And CaO-MgO-SiO 2 Etc., among which SiO is preferred 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 Or a combination thereof. The precursor of the inorganic refractory oxide has a usual meaning in the art, and means any material that can be converted into an inorganic refractory oxide during the production method of the present invention (for example, by a firing step described below), and examples thereof include aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum isopropoxide, sodium silicate, ethyl orthosilicate, silica sol, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, and the like, preferably aluminum nitrate, aluminum chloride, aluminum sulfate, sodium silicate, ethyl orthosilicate, magnesium nitrate, calcium nitrate, and more preferably aluminum nitrate, aluminum sulfate, sodium silicate, and magnesium nitrate.
According to the present invention, the amount of the carrier at this time is not particularly limited, but the carrier is preferably used in such an amount that the weight ratio of the composite oxide A to the carrier (in terms of inorganic refractory oxide) is 0.01 to 5:1, preferably 0.5 to 4:1, more preferably 1 to 3:1.
According to the present invention, as the Ce source, for example, there may be mentioned oxides, hydroxides, mineral acid salts and organic acid salts of Ce (including hydrates of these compounds), among which water-soluble mineral acid salts and water-soluble organic acid salts of Ce are preferable, and nitrate and acetate salts of Ce are more preferable, for example, ce (NO 3 ) 3 Or a hydrate thereof.
According to the present invention, as the Fe source, for example, there may be mentioned oxides, hydroxides, inorganic acid salts and organic acid salts of Fe (including hydrates of these compounds), among which water-soluble inorganic acid salts and water-soluble organic acid salts of Fe are preferable, and nitrate and acetate of Fe are more preferable, for example, fe (NO 3 ) 3 Or a hydrate thereof.
According to the present invention, as the Ti source, for example, there can be mentioned oxides, hydroxides, inorganic acid salts and organic acid salts of Ti (including hydrates of these compounds), among which water-soluble inorganic acid salts and water-soluble organic acid salts of Ti are preferable, and sulfate and acetate of Ti are more preferable, for example, ti 2 (SO 4 ) 3 Or a hydrate thereof.
According to a preferred embodiment of the present invention, the Ce source, the Fe source, the Ti source are provided in the form of aqueous solutions, and the composite oxide a is obtained by mixing these aqueous solutions (sequentially or simultaneously) to react, optionally in the presence of the support.
According to the present invention, the reaction of the Ce source, the Fe source, the Ti source is preferably performed in the presence of stirring.
According to the present invention, the Ce source, the Fe source, and the Ti source are generally under the following reaction conditions: the pH value of the reaction system is 7-10, preferably 7.5-9, the reaction temperature is 60-90 ℃, preferably 70-80 ℃, and the reaction time is 1-12 hours, preferably 3-10 hours.
After manufacture, the composite oxide a of the present invention may also be shaped into a suitable particle form, such as a bar, a sheet, a column, a sphere, a zigzag, etc., according to the techniques known in the art, as required. For example, the composite oxide A is mixed with a binder (preferably pseudo-boehmite) and kneaded to form a desired product.
The production method according to the present invention, although not necessarily, optionally further includes a step of partially reducing the composite oxide a (α=0) to an α of more than 0 to δ/2, preferably more than 0 to δ/4, in which case the composite oxide is also referred to as composite oxide B.
The manner of carrying out the partial reduction is not limited in accordance with the present invention, as long as a part of the metal elements in the composite oxide A can be brought into a reduced valence state (such as Ce 0 、Fe 2+ Or Ti (Ti) 0 Etc.). The kind of the metal element in which the partial reduction occurs is not particularly limited in the present invention.
According to the present invention, by this partial reduction, a CeFe for composition can be obtained x Ti y O δ-α The composite oxide B represented wherein α is greater than 0 to δ/2, preferably greater than 0 to δ/4, and the other symbols are as previously described.
According to the present invention, the partial reduction method may be, for example, a method in which the composite oxide a is brought into contact with a reducing agent (for example, hydrogen gas) under appropriate reaction conditions to cause a reduction reaction. Examples of the reaction conditions include: the reaction temperature is 60-600 ℃, the reaction pressure is 15-1500psia, and the reaction time (e.g., 0.5-12 hours, but sometimes without limitation) sufficient to partially reduce the complex oxide a to an alpha greater than 0 to delta/2, preferably greater than 0 to delta/4.
According to the present invention, the composition of the composite oxide (including composite oxide a and composite oxide B) can be identified by atomic emission spectrometry (ICP) or X-ray fluorescence spectrometry (XRF).
According to a preferred embodiment of the present invention, the Ce source, the Fe source, and the Ce source are subjected to a coprecipitation reaction (neutralization reaction) by the contact, thereby obtaining a composite oxide a.
According to the method of the present invention, the Ce source, the Fe source, the Ti source are provided in the form of aqueous solutions, which are mixed (sequentially or simultaneously) optionally in the presence of the support, to undergo a co-precipitation reaction to obtain an aqueous slurry.
For example, the Ce source, the Fe source, and the Ti source are dissolved in water to prepare respective aqueous solutions, and these aqueous solutions and optionally the carrier are added to a reaction system (such as a reaction vessel) in a predetermined amount sequentially or simultaneously (preferably, the carrier is added first) under stirring, the pH of the reaction system is adjusted to 7 to 10 (preferably, 7.5 to 9, such as using an aqueous ammonia solution), and coprecipitation is performed at a reaction temperature of 60 to 90 ℃ (preferably, 70 to 80C) for 1 to 12 hours (preferably, 3 to 10 hours), thereby obtaining the aqueous slurry.
The composite oxide a is then obtained by dewatering, optionally shaping, drying and calcining the aqueous slurry.
According to the present invention, the dehydration may be performed in a manner known in the art, for example, evaporation dehydration method, filtration dehydration method, or the like.
According to the invention, the shaping can be carried out in a manner known in the art (e.g. extrusion, granulation) in order to obtain a composite oxide A having a suitable particle morphology (e.g. bar, flake, column, sphere, etc.).
According to the present invention, the drying may be performed in a manner known in the art, and examples thereof include a spray drying method, a vacuum drying method, a thermal oven drying method, and the like. The drying and the shaping may be performed as one step, as required. As the conditions for the drying, for example, a drying temperature of 60 to 180℃and preferably 100 to 150℃and a drying time of 4 to 48 hours, preferably 6 to 36 hours and more preferably 8 to 24 hours can be mentioned.
According to the present invention, the dried aqueous slurry is completely converted into the composite oxide a by the firing while the precursor of the inorganic refractory oxide (when in use) is converted into the inorganic refractory oxide. As the conditions for the calcination, for example, a calcination temperature of 600 to 1200 ℃, preferably 700 to 1100 ℃, more preferably 800 to 1050 ℃, and a calcination time of 3 to 12 hours, preferably 4 to 10 hours can be cited. The calcination may be performed in an oxygen-containing atmosphere (such as air) as needed.
According to the invention, the use of the aforementioned composite oxides according to the invention as chemical looping combustion catalysts is also disclosed. In particular, the invention relates to a method for producing hydrogen by chemical looping combustion, which comprises the step of producing hydrogen by chemical looping combustion by taking the composite oxide disclosed by the invention as a catalyst.
According to the invention, the reaction conditions of the chemical looping combustion are: the reaction temperature of the composite oxide in the fuel is 500-800 ℃, the reaction temperature of the composite oxide in the water vapor is 500-800 ℃, and the fuel can be solid fuel or gaseous fuel.
The invention relates to CeFe for carrying the composition of the composite oxide x Ti y O δ-α And is represented by x=5 to 35, y=1 to 25, and δ is a positive number representing a value when oxygen in the composite oxide reaches a valence state equilibrium, α=0 to δ/2. The oxygen carrier has the advantages of high oxygen carrying rate, stable cyclic reactivity, high hydrogen production efficiency, simple preparation process, good repeatability and the like, can bear higher reaction temperature, and is suitable for industrial production.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When the specification describes a material, method, component, apparatus or device in any other form known to those skilled in the art or as commonly known in the art, that term is intended to include the use of that term as conventionally employed in the art at the time of filing this application, but also includes what is presently not commonly employed but would become known in the art to be suitable for like purposes.
Furthermore, the various ranges mentioned in this specification are inclusive of their endpoints unless explicitly stated otherwise. Furthermore, when an amount, concentration, or other value or parameter is given a range, one or more preferred ranges or many upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such value pairs are disclosed.
Finally, unless explicitly indicated otherwise, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise specified, as such, do not conform to the routine knowledge of one skilled in the art.
Example 1
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, heating to 70 ℃, slowly dropwise adding concentrated ammonia water into the solution under stirring to ensure that the pH value of the slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to neutrality, and obtaining the productThe obtained sample was dried, calcined at 100℃for 24 hours. The calcination temperature was 580℃and the calcination time was 8 hours. Obtaining the final composite oxide with the composition of CeFe 18 Ti 5 O 39 Denoted as C1.
Example 2
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, heating to 80 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 9, standing and aging for 10 hours after complete precipitation, filtering, repeatedly washing with deionized water to neutrality, and drying, roasting, wherein the drying temperature is 150 ℃ and the drying time is 8 hours. The roasting temperature is 680 ℃ and the roasting time is 4 hours. CeFe for obtaining final composite oxide composition 24 Ti 15 O 68 Denoted C2.
Example 3
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 Denoted C3.
Example 4
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 And (3) representing. Will be compoundedOxide and Al 2 O 3 Uniformly mixing according to the mass ratio of 1:1, extruding, molding, drying, roasting, wherein the drying temperature is 100 ℃, the drying time is 24 hours, the roasting temperature is 800 ℃, the roasting time is 10 hours, and the obtained sample is marked as C4
Example 5
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 And (3) representing. Combining the composite oxide with MgO-Al 2 O 3 Uniformly mixing according to the mass ratio of 2:1, extruding, molding, drying and roasting, wherein the drying temperature is 150 ℃, the drying time is 8 hours, the roasting temperature is 1050 ℃, the roasting time is 4 hours, and the obtained sample is marked as C5.
Example 6
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 And (3) representing. Combining the composite oxide with MgO-Al 2 O 3 Uniformly mixing according to the mass ratio of 3:1, extruding, molding, drying and roasting, wherein the drying temperature is 120 ℃, the drying time is 12 hours, the roasting temperature is 900 ℃, the roasting time is 6 hours, and the obtained sample is marked as C6.
Example 7
Weighing a certain amount of ferric nitrate, cerium nitrate and sulfurDissolving titanium protoxide in deionized water, adding carrier SiO after complete dissolution 2 Then heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The roasting temperature is 1000 ℃ and the roasting time is 6 hours. Obtaining the final composition of CeFe 20 Ti 10 O 52 - SiO 2 Is C7, the CeFe 20 Ti 10 O 52 Composite oxide and carrier SiO 2 The mass ratio of (2) is 1:1.
Example 8
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, and adding a carrier MgO-SiO after complete dissolution 2 Then heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The roasting temperature is 900 ℃ and the roasting time is 6 hours. Obtaining the final composition of CeFe 20 Ti 10 O 52 / MgO-SiO 2 Is designated C8, the CeFe 20 Ti 10 O 52 With a carrier MgO-SiO 2 The mass ratio of (2) is 1:1.
Example 9
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 And (3) representing. Subjecting the obtained composite oxide to pressureThe sample obtained was partially reduced at 1000psia and a temperature of 400℃for 4 hours using CeFe of formula 20 Ti 10 O 10 Denoted C9.
Example 10
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying the obtained sample, wherein the drying temperature is 120 ℃ and the drying time is 12 hours. The calcination temperature was 600℃and the calcination time was 6 hours. CeFe for obtaining final composite oxide composition 20 Ti 10 O 52 And (3) representing. Combining the composite oxide with Al 2 O 3 Uniformly mixing according to a mass ratio of 2:1, extruding, molding, drying, roasting at 120 ℃ for 12 hours at 900 ℃ for 6 hours, and partially reducing the obtained composite oxide for 2 hours under the condition of 1000psia and 600 ℃ to obtain the CeFe for the sample 20 Ti 10 O 20 /Al 2 O 3 Denoted C10.
Comparative example 1
And (3) weighing a certain amount of ferric nitrate and titanium sulfite to be dissolved in deionized water, heating to 70 ℃ according to the molar ratio of 18:1, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying, roasting, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. The calcination temperature was 580℃and the calcination time was 8 hours. The final composite oxide was obtained and designated as C11.
Comparative example 2
And (3) weighing a certain amount of ferric nitrate and cerium nitrate, dissolving in deionized water, heating to 70 ℃ with the molar ratio of iron ions to cerium ions being 18:1, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to neutrality, and drying, roasting, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. The calcination temperature was 580℃and the calcination time was 8 hours. The final composite oxide was obtained and designated as C12.
Example 1
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfite, dissolving in deionized water, heating to 70 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, and drying, roasting, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. The calcination temperature was 580℃and the calcination time was 8 hours. Obtaining the final composite oxide with the composition of CeFe 18 Ti 5 O 39 Denoted as C1.
The evaluation of the catalyst performance prepared in the above examples was performed as follows. The catalyst evaluation test was carried out in a continuous flow fixed bed reactor, 3ml of oxygen carrier was taken and mixed with quartz sand of the same mesh number in a volume ratio of 1:1. The fuel gas was methane (10 vol% CH) 4 ，90vol%N 2 ) The flow rate is 220ml/min, the reaction temperature is 900 ℃, and the reaction pressure is normal pressure. After 5 minutes of reduction, the temperature was kept at 900 ℃ for 20 minutes by switching to nitrogen. Then water is introduced, gasified first and then enters a preheater, the temperature of which is kept at 300 ℃, and then enters the reactor. After the reaction was completed, the water supply was stopped, the air supply was started at a flow rate of 25ml/min, and the temperature was maintained at 900 ℃. After 10 minutes of reaction, the reaction mixture was again switched to nitrogen, and the temperature was kept unchanged. And then fuel gas is introduced, and the reaction conditions are consistent with the reduction reaction conditions. The molecular sieve 5A column and the PorapakQ column are adopted for online analysis by 7890 type gas chromatography, and TCD detection is carried out. The results of the performance evaluation are shown in Table 1.
TABLE 1 reactivity of catalysts
*1: cycling 50 times of CH 4 Average conversion of (2);
*2: cycling 100 times CH 4 Average conversion of (2);
*3: single H when circulating 100 times 2 Average value of yield.
Claims (27)
1. A method of chemically firing hydrogen comprising: the composite oxide is used as a catalyst to prepare hydrogen through chemical looping combustion; ceFe for the composition of the composite oxide x Ti y O δ-α And is represented by x=15 to 35, y=1 to 25, and δ is a positive number representing a value when oxygen in the composite oxide reaches a valence state equilibrium, α=0 to δ/2.
2. The method according to claim 1, characterized in that: and x is 15-30.
3. The method according to claim 2, characterized in that: and x is 15-25.
4. The method according to claim 2, characterized in that: and x is 18-24.
5. The method according to claim 1, characterized in that: and y is 3-20.
6. The method according to claim 5, wherein: and y is 5-15.
7. The method according to claim 1, characterized in that: alpha is 0 to delta/4.
8. The method according to claim 7, wherein: alpha is 0.
9. The method according to claim 1, characterized in that: the composite oxide is supported on a carrier.
10. The method according to claim 9, wherein: the carrier is SiO 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 、Al 2 O 3 -SiO 2 、CaO-SiO 2 、CaO-MgO-SiO 2 Or a combination thereof.
11. The method according to claim 10, wherein: the carrier is SiO 2 、Al 2 O 3 、MgO-SiO 2 、MgO-Al 2 O 3 Or a combination thereof.
12. The method according to claim 9, wherein: the weight ratio of the composite oxide to the carrier is 0.01-5:1.
13. The method according to claim 12, wherein: the weight ratio of the composite oxide to the carrier is 0.5-4:1.
14. The method according to claim 12, wherein: the weight ratio of the composite oxide to the carrier is 1-3:1.
15. The method according to claim 1, characterized in that: the preparation method of the composite oxide comprises the step of contacting a Ce source, a Fe source and a Ti source to react to obtain the composite oxide.
16. The method according to claim 15, wherein: the contacting is performed in the presence of a carrier, thereby supporting the composite oxide on the carrier.
17. The method according to claim 15, wherein: the Ce source is oxide, hydroxide, inorganic acid salt or organic acid salt of Ce.
18. The method according to claim 15, wherein: the Fe source is oxide, hydroxide, inorganic acid salt or organic acid salt of Fe.
19. The method according to claim 15, wherein: the Ti source is oxide, hydroxide, inorganic acid salt or organic acid salt of Ti.
20. The method according to claim 15, wherein: the Ce source, the Fe source, and the Ti source are provided in the form of aqueous solutions, and the composite oxide is obtained by mixing these aqueous solutions, one after the other or simultaneously, optionally in the presence of a carrier, to react.
21. The method according to claim 15, wherein: the reaction of the Ce source, the Fe source, the Ti source is performed in the presence of stirring.
22. The method according to claim 15, wherein: the reaction conditions of the Ce source, the Fe source and the Ti source when the reaction is carried out are as follows: the pH value of the reaction system is 7-10, the reaction temperature is 60-90 ℃, and the reaction time is 1-12 hours.
23. The method according to claim 15, wherein: the reaction conditions of the Ce source, the Fe source and the Ti source when the reaction is carried out are as follows: the pH value of the reaction system is 7.5-9, the reaction temperature is 70-80 ℃ and the reaction time is 3-10 hours.
24. The method according to claim 15, wherein: the composite oxide is shaped into a bar, a sheet, a column, a sphere or a zigzag as required.
25. The method according to claim 15, wherein: comprising the step of partially reducing the complex oxide α=0 to a value of α greater than 0 to δ/2.
26. The method according to claim 15, wherein: comprising the step of partially reducing the complex oxide α=0 to a value of α greater than 0 to δ/4.
27. The method according to claim 25, wherein: the reduction conditions were as follows: the reaction temperature is 60-600 ℃, the reaction pressure is 15-1500psia, and the reaction time is enough to partially reduce the composite oxide A to alpha greater than 0 to delta/2.
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